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Synthesis and characterization of organotin complexes with 2‐mercaptopyridine derivatives
Author(s) -
Couce M. D.,
Cherchi V.,
Faraglia G.,
Russo U.,
Sindellari L.,
Valle G.,
Zancan N.
Publication year - 1996
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/(sici)1099-0739(199602)10:1<35::aid-aoc475>3.0.co;2-d
Subject(s) - chemistry , trigonal bipyramidal molecular geometry , bond length , molecular geometry , denticity , crystallography , octahedron , isopropyl , stereochemistry , adduct , octahedral molecular geometry , single bond , tin , crystal structure , medicinal chemistry , molecule , organic chemistry , alkyl
By reaction of diphenyltin(IV) chloride and triphenyltin(IV) hydroxide with esters of the 2‐mercaptopyridine‐5‐carboxylic acid (OVERBAR)NH(CS)CHCHC(COOR)(/OVERBAR)CH (HTNME, R = methyl; HTNEE, R = ethyl; HTNIPE, R = isopropyl) the complexes Ph 3 Sn(L), Ph 2 SnCI(L) (L = TNME, TNEE and TNIPE) and Ph 2 Sn(TNEE) 2 have been prepared and characterized by IR, NMR and Mössbauer spectroscopies. Moreover, the Ph 2 SnCl 2 /2‐mercaptopyridine (HMP) system has been found to yield either the Ph 2 SnCl 2 (HMP) 2 adduct or the Ph 2 SnCl(MP) complex. The structures of Ph 2 SnCl(TNEE) and Ph 2 SnCl(MP) have been determined by X‐ray single‐crystal diffraction studies. The two structures are similar. Both ligands behave as bidentate chelating groups forming a four‐membered ring with an identical small N(SINGLE BOND)Sn(SINGLE BOND)S bite angle of 63.7°. The tin atom is pentacoordinated, presenting a severely distorted trigonal bipyramidal geometry with apical Cl(SINGLE BOND)Sn(SINGLE BOND)N angles of 155.0(2)° [Ph 2 SnCl(TNEE)] and 155.7(7)° [Ph 2 SnCl(MP)] and equatorial C(SINGLE BOND)Sn(SINGLE BOND)C angles of 114.9(2)° and 125.0(3)° respectively. On the basis of 119 Sn Mössbauer data, all the complexes should present analogous structures except Ph 2 Sn(TNEE) 2 and Ph 2 SnCl 2 (HMP) 2 , for which an octahedral coordination geometry with a trans arrangement of the phenyl groups can be proposed. The effect of dimethyl sulphoxide on Ph 2 SnCl(L) and Ph 2 SnCl 2 (HMP) 2 is also discussed.